Unusual substrates for cascade reactions: Racemic β-ketoesters with all-carbon quaternary centers were used as starting materials in a dynamic kinetic resolution process to produce complex polycycles in high enantio- and diastereoselectivities (see scheme; TBS=tert-butyldimethylsilyl). The cascade reactions involved epimerization in the second step through the formation and cleavage of multiple CC bonds in a retro-aldol/aldol equilibrium.
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Xu et al. (2005) studied this question.
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